This invention relates to a process for preparing a catalyst component that is useful for olefin polymerization or interpolymerization. In particular the catalyst component comprises magnesium, titanium, vanadium compounds and an electron donor.
Many catalysts are known for producing polyolefins having desired properties. Mixed metal catalysts of varying transition metals are used in producing polyolefins. In particular the use of mixed metal catalysts containing vanadium and titanium catalysts have been described in patents for such purpose. For example such patents include U.S. Pat. Nos. 6,084,042; 5,691,264; 5,442,018; 5,420,090; 5,231,151; 5,227,354; 5,106,805; 5,075,271; 5,059,570; 5,034,483; 5,013,701; 5,006,618; 5,006,499; 4,912,074; 4,831,000; 4,814,314; 4,612,300; 4,537,869; 4,506,029; and 4,471,066. The patents describe various types of catalysts and use of the catalysts for preparing polyolefins having various properties.
A process for preparing a catalyst component comprising titanium, vanadium, magnesium chloride and at least one electron donor (ED), both supported and unsupported. The process for preparing the catalyst component comprises contacting magnesium chloride with a vanadium compound containing at least one electron donor thereby yielding a product that is thereafter contacted with a titanium compound, wherein the amounts of the magnesium, titanium and vanadium are specifically defined. The resulting catalyst component, with a cocatalyst, provides a catalyst system suitable for the polymerization or interpolymerization of olefins.
A process for preparing a catalyst component comprising titanium, vanadium, magnesium chloride and at least one electron donor (ED), both supported and unsupported. The process for preparing the catalyst component comprises contacting magnesium chloride with a vanadium compound containing at least one electron donor thereby yielding a product that is thereafter contacted with a titanium compound, wherein the amounts of the magnesium, titanium and vanadium are specifically defined. The resulting catalyst component, with a cocatalyst, provides a catalyst system suitable for the polymerization or interpolymerization of olefins.
All mention herein to elements of Groups of the Periodic Table are made in reference to the Periodic Table of the Elements, as published in xe2x80x9cChemical and Engineering Newsxe2x80x9d, 63(5), 27, 1985. In this format, the Groups are numbered 1 to 18.
In the process for preparing the catalyst component, any magnesium chloride may be used. It has been found that the magnesium chloride may be utilized in the form of magnesium chloride supported on silica such as Sylopol 5550 support obtainable from Grace-Davison. Sylopol 5550 support is described as magnesium chloride supported on silica, containing 3.53 wt % magnesium and a molar ratio of chlorine to magnesium of 2.02.
In the present process there is used a vanadium compound containing at least one electron donor. The vanadium compounds that are usable herein are selected from OVXm(OR)3xe2x88x92m(ED)s; OVXm(NR2)3xe2x88x92m(ED)s; VXn(OR)4xe2x88x92n(ED)s; VXn(NR2)4xe2x88x92n(ED)s; [V3O(RCO2)6]2.[V2O2X6(ED)s]; [V(CO)3(ED)s].[V(CO)6]; M[V(bipy)2].(ED)s; M3[V(C2O4)3].(ED)s; M[VOX4].(ED)s; V3O(RCO2)6(ED)s; O3xe2x88x92pVRxe2x80x2p(ED)S; VXmRxe2x80x23xe2x88x92m(ED)s; VX2.(ED)s; OVXqRxe2x80x2r(ED)S wherein m is 0 to 3, n is 0 to 4, p is 1 to 3, q is 0 to 2, r is 0 to 2, q is not equal to r, s is greater than 0, preferably s is from about 0.1 to about 3, X is independently fluorine, chlorine, bromine or iodine, R is independently a C1-C18 acyclic or cyclic hydrocarbon radical, ED is an electron donor, M is a cation of lithium, sodium, potassium or cesium (Li+, Na+, K+ or Cs+), bipy is 2,2xe2x80x2-bipyridine and Rxe2x80x2 is a monoanionic bidentate ligand.
With respect to the above described vanadium compounds containing at least one electron donor, suitable for use as acyclic or cyclic radicals (R) are C1-18 alkyl, C2-18 alkenyl, C4-18 dienyl, C3-18 cycloalkyl, C3-18 cycloalkenyl, C4-18 cyclodienyl, C6-18 aryl, C7-18 aralkyl, and C7-18 alkaryl.
Further with respect to the above described vanadium compounds containing at least one electron donor, the electron donors suitable for use herein include carboxylic acid esters, anhydrides, acid halides, ethers, alcohols, thiols, thioethers, aldehydes, ketones, imines, amines, amides; nitrites, isonitriles, cyanates, isocyanates, thiocyanates, isothiocyanates, thioesters, dithioesters, carbonic esters, hydrocarbyl carbamates, hydrocarbyl thiocarbamates, urethanes, sulfoxides, sulfones, sulfonamides, organosilicon compounds containing at least one oxygen atom, and nitrogen, phosphorous, arsenic or antimony compounds connected to an organic group through a carbon or oxygen atom. More preferred as electron donors are compounds containing from 1 to 50 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 14, 15, 16 and 17 of the Periodic Table of Elements. Most preferred for use is an ether such as tetrahydrofuran.
Further with respect to the above described vanadium compounds containing at least one electron donor, suitable for use herein as the monoanionic bidentate ligand (Rxe2x80x2) are the Lewis bases of the following compounds which contain acidic hydrogen; carboxylic acids, carboxylic acid amides, carboxylic acid phosphides, thiocarboxylic acids, dithiocarboxylic acids, thiocarboxylic acid amides, thiocarboxylic acid phosphides, carbonic acid, carbamamic acids, ureas, thiocarbonic acid, thioureas, thiocarbamamic acids, dithiocarbamic acids, hydroxycarboxylic esters, hydroxycarboxylic acid amides, amino acid esters, hydroxythiocarboxylic esters, hydroxydithiocarboxylic esters, hydroxythiocaboxylic acid amides, hydroxycarboxylic thioesters, hydroythiocarboxylic thioesters, hydroxydithiocarboxylic thioesters, mercaptocarboxylic esters, mercaptocarboxylic acid amides, mercaptothiocarboxylic esters, mercaptodithiocarboxylic esters, mercaptothiocarboxylic acid amides, mercaptocarboxylic thioesters, mercaptothiocarboxylic thioesters, mercaptodithiocarboxylic thioesters, hydroxyketones, hydroxyaldehydes, hydroxyimines, mercaptoketones, mercaptoaldehydes, mereaptoimines, hydroxythioketones, hydroxythioaldehydes, mercaptothioketones, mercaptothioaldehydes, 2-hydroxybenzaldehydes, 2-mercaptobenzaldehydes, 2-aminobenzaldehydes, 2-hydroxybenzthioaldehydes, 2-hydroxybenzoate esters, 2-hydroxybenzamides, 2-hydroxybenzoate thioesters, 2-hydroxythiobenzoate esters, 2-hydroxythiobenzamides, 2-hydroxybenzthioaldehydes, 2-mercaptobenzthioaldhydes, 2-aminobenzthioaldehydes, 2-hydroxyarylketones, 2-mercaptoarylketones, 2-aminoarylketones, 2-hydroxyarylimines, 2-mercaptoarylimines, 2-aminoarylimines, 2-hydroxyarylthioketones, 2-mercaptoarylthioketones, 2-aminoarylthioketones, benzoins, 2-pyrrolecarboxaldehydes, 2-pyrrolethiocarboxyaldehydes, 2-pyrrolecarboxaldimines, hydrocarbyl 2-pyrrolyl ketones, hydrocarbyl 2-pyrrolylimines, hydrocarbyl 2-pyrrolyl thioketones, 2-indolecarboxaldehydes, 2-indolethiocarboxaldehydes, 2-indolecarboxaldimines, hydrocarbyl 2-indolyl ketones, hydrocarbyl 2-indolyl imines, hydrocarbyl 2-indolyl thioketones, hydroxyquinolines, tropolones, aminotropolones, aminotropone imines, and the like.
Preferred for use herein as the vanadium compound containing an electron donor are VCl3.zTHF (z=2-3), VOCl3.THF, and VOF3.THF.
The vanadium compounds containing at least one electron donor may be prepared by any method known in the art. For example, a vanadium compound may be dissolved in excess electron donor and the excess electron donor subsequently removed.
In the present process the titanium compound is selected from TiXa(OR)4xe2x88x92a; TiXa(NR2)4xe2x88x92a; Ti(NR2)4xe2x88x92aRxe2x80x2a; TiX4xe2x88x92aRxe2x80x2a; Ti(OR)4xe2x88x92aRxe2x80x2a; OTiRxe2x80x22; TiXb(ED)c; H2TiX6; (Bpy3)TiX3; wherein X is independently fluorine, chlorine, bromine or iodine; R is independently a C1-C18 acyclic or cyclic hydrocarbon radical; Rxe2x80x2 is independently a monoanionic bidentate ligand; a is 0 to 4; b is an integer greater than 0, preferably 1 to 100; c is an integer greater than 0, preferably 1 to 100; ED is an electron donor; Bpy3 is trispyrazole borate.
With respect to the above described titanium compounds, suitable for use as acyclic or cyclic radicals (R) are C1-18 alkyl, C2-18 alkenyl, C4-18 dienyl, C3-18 cycloalkyl, C3-18 cycloalkenyl, C4-18 cyclodienyl, C6-18 aryl, C7-18 and C7-18 alkaryl.
Further, with respect to the above described titanium compounds suitable for use herein as the monoanionic bidentate ligand (Rxe2x80x2) are the Lewis bases of the following compounds which contain acidic hydrogen; carboxylic acids, carboxylic acid amides, carboxylic acid phosphides, thiocarboxylic acids, dithiocarboxylic acids, thiocarboxylic acid amides, thiocarboxylic acid phosphides, carbonic acid, carbamamic acids, ureas, thiocarbonic acid, thioureas, thiocarbamamic acids, dithiocarbamic acids, hydroxycarboxylic esters, hydroxycarboxylic acid amides, amino acid esters, hydroxythiocarboxylic esters, hydroxydithiocarboxylic esters, hydroxythiocaboxylic acid amides, hydroxycarboxylic thioesters, hydroythiocarboxylic thioesters, hydroxydithiocarboxylic thioesters, mercaptocarboxylic esters, mercaptocarboxylic acid amides, mercaptothiocarboxylic esters, mercaptodithiocarboxylic esters, mercaptothiocarboxylic acid amides, mercaptocarboxylic thioesters, mercaptothiocarboxylic thioesters, mercaptodithiocarboxylic thioesters, hydroxyketones, hydroxyaldehydes, hydroxyimines, mercaptoketones, mercaptoaldehydes, mercaptoimines, hydroxythioketones, hydroxythioaldehydes, mercaptothioketones, mercaptothioaldehydes, 2-hydroxybenzaldehydes, 2-mercaptobenzaldehydes, 2-aminobenzaldehydes, 2-hydroxybenzthioaldehydes, 2-hydroxybenzoate esters, 2-hydroxybenzamides, 2-hydroxybenzoate thioesters, 2-hydroxythiobenzoate esters, 2-hydroxythiobenzamides, 2-hydroxybenzthioaldehydes, 2-mercaptobenzthioaldhydes, 2-aminobenzthioaldehydes, 2-hydroxyarylketones, 2-mercaptoarylketones, 2-aminoarylketones, 2-hydroxyarylimines, 2-mercaptoarylimines, 2-aminoarylimines, 2-hydroxyarylthioketones, 2-mercaptoarylthioketones, 2-aminoarylthioketones, benzoins, 2-pyrrolecarboxaldehydes, 2-pyrrolethiocarboxyaldehydes, 2-pyrrolecarboxaldimines, hydrocarbyl 2-pyrrolyl ketones, hydrocarbyl 2-pyrrolylimines, hydrocarbyl 2-pyrrolyl thioketones, 2-indolecarboxaldehydes, 2-indolethiocarboxaldehydes, 2-indolecarboxaldimines, hydrocarbyl 2-indolyl ketones, hydrocarbyl 2-indolyl imines, hydrocarbyl 2-indolyl thioketones, hydroxyquinolines, tropolones, aminotropolones, aminotropone imines, and the like.
Further, with respect to the above described titanium compounds, the electron donors suitable for use herein include carboxylic acid esters, anhydrides, acid halides, ethers, alcohols, thiols, thioethers, aldehydes, ketones, imines, amines, amides, nitriles, isonitriles, cyanates, isocyanates, thiocyanates, isothiocyanates, thioesters, dithioesters, carbonic esters, hydrocarbyl carbamates, hydrocarbyl thiocarbamates, urethanes, sulfoxides, sulfones, sulfonamides, organosilicon compounds containing at least one oxygen atom, and nitrogen, phosphorous, arsenic or antimony compounds connected to an organic group through a carbon or oxygen atom. More preferred as electron donors are compounds containing from 1 to 50 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 14, 15, 16 and 17 of the Periodic Table of Elements. Exemplary titanium compounds suitable for use herein include, TiCl4, TiBr4, Til4, TiF4, TiCl3, TiF3, Ti(OC2H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(O-iC3H7)Cl3, Ti(O-n-C4H9)Cl3, Ti(O-n-C4H9)2Cl2, Ti(OC2H5)Br3, Ti(OC2H5)2(OC4H9)Cl, Ti(OC6H5)Cl3, Ti(O-i-C4H9)Cl3, Ti(OC5H11)Cl3, Ti(OC6H13)Cl3, Ti(OC2H5)4, Ti(O-n-C3H7)4, Ti(O-i-C3H7)4, Ti(O-n-C4H9)4, Ti(O-i-C4H9)4, Ti(O-n-C6H13)4, Ti(O-n-C8H17)4, Ti(OCH2CH(C2H5)C4H9)4, Bis(2,2,6,6tetramethyl-3,5-heptanedionato)oxotitanium, Dichlorobis(2,2,6,6-teramethyl-3,5-heptanedionato titanium, Di(i-propoxide)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium(IV), hexafluorotitanic acid, Hydrotris(1-pyrazolylborato)trichlorotitaium(IV), tetrachlorobis(cyclohexylmercapto)titanium(IV), tetrachlorodiamminotitanium(IV), tetrachlorobis(tetrahydrofuran)titanium(IV), tetrakis(diethylamino)titanium, tetrakis(dimethylamino)titanium, titanium (IV) t-butoxide, titanium (di-ipropoxide)bis(acetylacetonate), titanium hydride, titanium (IV) oxide bis(acetylacetonate), trichlorotris(tetrahydrofuran)titanium(III), tris(2,2,6,6tetramethyl-3,5-heptanedionato)titanium (III).
The preferred titanium compound is (2,6-Di-tert-butyl-4-methylphenoxy)titanium(IV) trichloride [(BHTxe2x80x2)TiCl3].
The titanium compounds to be used herein, may be prepared by any method known in the art.
In the present process the quantities of magnesium, vanadium and titanium are as follows. The molar ratio of magnesium to vanadium ranges from about 2:1 to about 100:1. Preferably the molar ratio of magnesium to vanadium ranges from about 7:1 to about 80:1. Most preferably the molar ratio of magnesium to vanadium ranges from about 10:1 to about 40:1. The molar ratio of magnesium to titanium ranges from about 2:1 to about 100:1. Preferably the molar ratio of magnesium to titanium ranges from about 7:1 to about 80:1. Most preferably the molar ratio of magnesium to titanium ranges from about 10:1 to about 40:1. The molar ratio of titanium to vanadium ranges from about 0.1:1 to about 10:1. Preferably the molar ratio of titanium to vanadium ranges from about 0.2:1 to about 5:1. Most preferably the molar ratio of titanium to vanadium ranges from about 0.3:1 to about 3:1.
The catalyst component of the present process may be used either supported or unsupported. When used in a supported manner, any inorganic or organic support may be used.
Examples of suitable inorganic supports include metal oxides, metal hydroxides, metal halogenides or other metal salts, such as sulphates, carbonates, phosphates, nitrates and silicates. Exemplary of inorganic carriers suitable for use herein are compounds of metals from Groups 1 and 2 of the Periodic Table of the Elements, such as salts of sodium or potassium and oxides or salts of magnesium or calcium, for instance the chlorides, sulphates, carbonates, phosphates or silicates of sodium, potassium, magnesium or calcium and the oxides or hydroxides of, for instance, magnesium or calcium. Also suitable for use are inorganic oxides such as silica, titania, alumina, zirconia, chromia, boron oxide, silanized silica, silica hydrogels, silica xerogels, silica aerogels, and mixed oxides such as talcs, silica/chromia, silica/chromia/titania, silica/alumina, silica/titania, silica/magnesia, silica/magnesia/titania, aluminum phosphate gels, silica co-gels and the like. The inorganic oxides may contain small amounts of carbonates, nitrates, sulfates and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O and Li2O. Supports containing at least one component selected from the group consisting of SiO2 and Al2O3 or mixtures thereof as a main component are preferred.
Examples of suitable organic supports include polymers such as, for example, polyethylene, polypropylene, interpolymers of ethylene and alpha-olefins, polystyrene, functionalized polystyrene, polyamides and polyesters.
In further detail, the present process is carried out in the following manner. The process is preferably carried out in an inert atmosphere. The magnesium chloride, preferably on a silica support, is contacted with a vanadium compound containing at least one electron donor. The magnesium chloride may be used as a dry powder, or fluidized with a stream of inert gas or preferably suspended in an inert solvent. Preferably, the magnesium chloride is contacted with the vanadium compound containing one or more electron donors at a temperature ranging from about xe2x88x92100xc2x0 C. to about 100xc2x0 C., more preferably, from about 20xc2x0 C. to about 60xc2x0 C. The vanadium compound containing at least one electron donor, when contacted with the magnesium chloride, may be used in any form such as dissolved or suspended in an inert solvent or used in the vapor, liquid or solid form. Preferably, the vanadium compound containing one or more electron donors is dissolved in an inert solvent prior to contacting the magnesium chloride. The magnesium chloride and vanadium compound containing at least one electron donor are mixed until there is obtained a product having a molar ratio of magnesium to vanadium ranging from about 2:1 to about 100:1. The resulting vanadium compound containing at least one electron donor and magnesium chloride, may be used in any form such as a dry powder, or fluidized with a stream of inert gas or preferably suspended in an inert solvent.
The resultant vanadium compound containing at least one electron donor and magnesium chloride, is then contacted with a titanium compound. Preferably the vanadium compound containing at least one electron donor and magnesium chloride, is contacted with the titanium compound at a temperature ranging from about xe2x88x92100xc2x0 C. to about 100xc2x0 C., more preferably from about 20xc2x0 C. to about 60xc2x0 C. The titanium compound, when contacted with the vanadium compound containing at least one electron donor and magnesium chloride, may be used in any form such as dissolved or suspended in an inert solvent or used in the vapor, liquid or solid form. Preferably, the titanium compound is dissolved in an inert solvent prior to contacting the vanadium compound containing at least one electron donor and magnesium chloride. The vanadium compound containing at least one electron donor and magnesium chloride, is mixed with the titanium compound until there is obtained a product having a molar ratio of magnesium to titanium ranging from about 2:1 to about 100:1. The resulting product comprises magnesium chloride, vanadium, electron donor and titanium wherein the molar ratio of magnesium to vanadium is about 2:1 to about 100:1, the molar ratio of magnesium to titanium is from about 2:1 to about 100:1, and the molar ratio of titanium to vanadium is from about 0.1:1 to about 10:1. The resulting product may be used in any form.
Any inert solvent may be used in the present process. For example, saturated hydrocarbon such as pentane, hexane, heptane and the like are useful. Aromatic hydrocarbons such as benzene, toluene and xylenes may also be used. Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, trichlorofluoromethane and the like are also useful.
The present invention also provides a catalyst system comprising
(A) at least one catalyst component prepared as described above, and
(B) (B) at least one cocatalyst
The molar ratio of the cocatalyst to the titanium in the catalyst component is from about 0.1 to about 1000. Preferably, the molar ratio of the cocatalyst to the titanium in the catalyst component is from about 5 to about 800.
The cocatalyst used with the catalyst component made by the process of this invention can be any organometallic compound, or mixtures thereof, that can activate the catalyst component in the polymerization of olefins. In particular, the cocatalyst that is reacted with the catalyst component contains a metal of Groups I, 2, 11, 12, 13 and/or 14 of the above described Periodic Table of the Elements. Exemplary of such metals are lithium, magnesium, copper, zinc, boron, silicon and the like, and mixtures thereof.
Preferably the cocatalyst is at least one compound of the formula, XtERxe2x80x33xe2x88x92t or mixtures thereof, wherein X is independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; t ranges from 0 to 2; E is an element from Group 13 of the Periodic Table of Elements such as boron, aluminum and gallium; Rxe2x80x3 is a hydrocarbon group, containing from 1 to 100 carbon atoms and from 0 to 10 oxygen atoms, connected to E (the Group 13 element) by a carbon or oxygen bond.
Exemplary of the Rxe2x80x3 groups suitable for use herein are C1-100 alkyl, C1-100 alkoxy, C2-100 alkenyl, C4-100 dienyl, C3-100 cycloalkyl, C3-100 cycloalkoxy, C3-100 cycloalkenyl, C4-100 cyclodienyl, C6-100 aryl, C7-100 aralkyl, C7-100 aralkoxy and C7-100 alkaryl. Also exemplary of Rxe2x80x3 are the hydrocarbon groups containing from 1 to 100 carbon atoms and from 1 to 10 oxygen atoms.
Exemplary of the cocatalyst that may be used with the catalyst component in preparing the catalyst systems of the present invention where t=0 are trimethylaluminum; triethylborane; triethylgallane; triethylaluminum; tri-n-propylaluminum; tri-n-butylaluminum; tri-n-pentylaluminum; triisoprenylaluminum; tri-n-hexylaluminum; tri-n-heptylaluminum; tri-n-octylaluminum; triisopropylaluminum; diisobutylaluminum; tris(cylcohexylmethyl)aluminum; dimethylaluminum methoxide; dimethylaluminum ethoxide; diethylaluminum ethoxide and the like. Exemplary of compounds where t=1 are dimethylaluminum chloride; diethylaluminum chloride; di-n-propylaluminum chloride; di-n-butylaluminum chloride; di-n-pentylaluminum chloride; diisoprenylaluminum chloride; di-n-hexylaluminum chloride; di-n-heptylaluminum chloride; di-n-octylaluminum chloride; diisopropylaluminum chloride; diisobutylaluminum chloride; bis(cylcohexylmethyl) aluminum chloride; diethylaluminum fluoride; diethylaluminum bromide; diethylaluminum iodide; dimethylaluminum hydride; diethylaluminum hydride; di-n-propylaluminum hydride; di-n-butylaluminum hydride; di-n-pentylaluminum hydride; diisoprenylaluminum hydride; di-n-hexylaluminum hydride; di-n-heptylaluminum hydride; di-n-octylaluminum hydride; diisopropylaluminum hydride; diisobutylaluminum hydride; bis(cylcohexylmethyl)aluminum hydride; chloromethylaluminum methoxide; chloromethylaluminum ethoxide; chloroethylaluminum ethoxide and the like. Exemplary of compounds where t=2 are methylaluminum dichloride; ethylaluminum dichloride; n-propylaluminum dichloride; n-butylaluminum dichloride; n-pentylaluminum dichloride; isoprenylaluminum dichloride; n-hexylaluminum dichloride; n-heptylaluminum dichloride; n-octylaluminum dichloride; isopropylaluminum dichloride; isobutylaluminum dichloride; (cylcohexylmethyl)aluminum dichloride and the like. Also exemplary are alkylaluminum sesquialkoxides such as methylaluminum sesquimethoxide; ethylaluminum sesquiethoxide; n-butylaluminum sesquinbutoxide and the like. Also exemplary are alkylaluminum sesquihalides such as methylaluminum sesquichloride; ethylaluminum sesquichloride; isobutylaluminum sesquichloride; ethylaluminum sesquifluoride; ethylaluminum sesquibromide; ethylaluminum sesquiiodide and the like.
Preferred for use herein as cocatalysts are trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum; and dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride; diisobutylaluminum chloride, diethylaluminum bromide and diethylaluminum iodide; and alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-butylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquifluoride, ethylaluminum sesquibromide and ethylaluminum, sesquiiodide.
Most preferred for use herein as cocatalysts are trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum and dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diisobutylaluminum chloride and alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-butylaluminum sesquichloride and isobutylaluminum sesquichloride.
Mixtures of compounds of the above formula XtER3xe2x88x92t also can be utilized herein as the cocatalyst.
In a further aspect of the invention, there is provided a process for polymerizing or interpolymerizing olefins using the catalyst systems of the invention, which comprise a catalyst component and a cocatalyst set forth herein.
Preferably, the present invention provides a process for polymerizing ethylene and/or interpolymerizing ethylene and at least one or more other olefin(s) comprising contacting under polymerization conditions, the ethylene and/or ethylene and at least one or more olefin(s) with the catalyst system of the present invention. The olefins, for example, may contain from 2 to 16 carbon atoms. Included herein are homopolymers, copolymers, terpolymers, and the like of the olefin monomeric units. Particularly preferred for preparation herein by the process of the present invention are polyethylenes. Such polyethylenes are defined as homopolymers of ethylene and interpolymers of ethylene and at least one alphaolefin wherein the ethylene content is at least about 50% by weight of the total monomers involved. Exemplary alpha-olefins that may be utilized herein are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-hexadecene and the like. Also utilizable herein are polyenes such as 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, 1,5-cyclooctadiene, 5-vinylidene-2norbornene, 5-vinyl-2-norbornene, and olefins formed in situ in the polymerization medium. When olefins are formed in situ in the polymerization medium, the formation of polyethylenes containing long chain branching may occur. Mixtures of olefins may be used herein.
The polymerization or interpolymerization process of the present invention may be carried out using any conventional process. For example, there may be utilized polymerization or interpolymerization in suspension, in solution, in super critical fluid or in gas phase media. All of these polymerization or interpolymerization processes are well known in the art.
Any additive used in polymerization processes may be utilized in the present polymerization processes. For example there may be incorporated external electron donors and/or molecular weight control agents such as hydrogen. Further, in the polymerization process there can be introduced any compound that increases the activity of the catalyst system such as halogenated hydrocarbons, oxygen, peroxides, hydroperoxides, quinones, ceric salts, cobalt(III) salts, stannic salts, calcium carbonate, organic nitrates, nitrites, azoxy compounds, organic polyvalent iodine compounds, organometallic complexes in a high valence state, alkyl disulfides and inorganic nitrogen-oxygen compounds. Still further, in the polymerization process there can be introduced any additive that lowers the molecular weight distribution of the resulting polymer, lowers the melting point of the resulting polymer, lowers the hexane extractables of the resulting polymer and/or lowers the static in the polymerization reactor. The olefin polymers or interpolymers of the present invention may be fabricated into films by any technique known in the art. For example, films may be produced by the well-known cast film, blown film and extrusion coating techniques.
Further, the olefin polymers or interpolymers may be fabricated into other articles of manufacture, such as molded articles, by any of the well-known techniques.
In the process of the invention, the catalyst component, cocatalyst or catalyst system can be introduced in any manner known in the art. For example, the catalyst component can be introduced directly into the polymerization or interpolymerization medium in the form of a slurry or dry free flowing powder. The catalyst component can also be used in the form of a prepolymer obtained by contacting the catalyst component with one or more olefins in the presence of a cocatalyst.